US4617240A - Coextruded film of polypropylene, polypropylene blend, and nylon - Google Patents
Coextruded film of polypropylene, polypropylene blend, and nylon Download PDFInfo
- Publication number
- US4617240A US4617240A US06/635,631 US63563184A US4617240A US 4617240 A US4617240 A US 4617240A US 63563184 A US63563184 A US 63563184A US 4617240 A US4617240 A US 4617240A
- Authority
- US
- United States
- Prior art keywords
- layer
- polypropylene
- nylon
- blend
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
- Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31746—Polymer of monoethylenically unsaturated hydrocarbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- This invention pertains to coextruded plastic films, and particularly, to those films having a polypropylene layer adhered to a layer of a nylon-type polyamide. In such films, the adhesion between the nylon and polypropylene layers has been particularly troublesome.
- an excellent adhesive for the coextrusion of nylon and polypropylene is a blend of a graft copolymer of maleic anhydride onto a polypropylene backbone, and an ungrafted polypropylene the graft copolymer having been produced in a reaction carried out at a temperature of from about 80° Celsius up to about 10° Celsius below the melting point of the polypropylene, the graft copolymer containing from about 0.10% to about 2.5% maleic anhydride based on the total weight of the graft copolymer, the graft copolymer comprising between about 5% and about 30% by weight of the blend.
- the graft copolymer reaction preferrably took place in the presence of an organic peroxide.
- the polypropylene layer may contain up to about 4% polymeric ethylene.
- the structure includes a fourth layer, of ethylene vinyl alcohol copolymer (EVOH), affixed on one of its surfaces to the nylon, and a fifth layer, of nylon, affixed to the other surface of the EVOH.
- EVOH ethylene vinyl alcohol copolymer
- the process comprises coextruding polypropylene, and nylon with the adhesive blend juxtaposed therebetween.
- the process comprises coextruding the five layer structure of, in sequential order in the structural layering, from one outside surface to the other: polypropylene, adhesive blend, nylon, EVOH, and nylon.
- FIG. 1 is a cross-section of a three layer coextruded structure of this invention.
- FIG. 2 is a cross-section of a five layer coextruded structure of this invention.
- FIG. 1 The most basic form of the invention is shown in the coextruded structure of FIG. 1, which is generally designated 10.
- the structure has three layers which are, respectively, a polypropylene layer 12, an adhesive blend layer of a maleic anhydride graft copolymer of polypropylene and an ungrafted polypropylene 14, and a nylon layer 16.
- Layer 12 may be a polypropylene homopolymer, a propylene ethylene copolymer, or a blend of polypropylene and polyethylene. In any event, the maximum acceptable ethylene content is about 20% by weight of the layer 12 composition.
- the polymer resin, or blends of resin, must, of course, be extrudable polymers.
- a preferred polymer for layer 12 is sold under the tradename of Hecules SA-752, which also contains about 4% ethylene.
- Another suitable polymer is Eastman 4G7DP, which contains small amounts of ethylene vinyl acetate.
- Layer 16 is a polymer, copolymer, or blend thereof selected from the nylon family of polyamides.
- Very desirable polymeric compositions for layer 16 are nylon 6, nylon 6,6, nylon 6, 6, 6, blends of nylon 6 with less than 25% nylon 12, blends of at least about 75% nylon 6 with any other polymer composition processable with nylon 6.
- materials which can be processed with nylon 6 as a blend are high density polyethylene, medium density polyethylene, low density polyethylene and polypropylene.
- an extrudable polymer may be satisfactorily used so long as it neither degrades at the processing temperature of about 500° F. to about 530° F., nor reacts appreciably with the nylon 6.
- Processing additives such as slip agents and the like may be satisfactorily used.
- Layer 14 serves as a coextruded adhesive layer between layers 12 and 16. It forms an inseparable bond with layer 12, and has good adhesion to layer 16.
- Layer 14 is a blend of two components: (1) a grafted copolymer of polypropylene and maleic anhydride and (2) an ungrafted polypropylene.
- the ungrafted polypropylene component (2) may be a polypropylene homopolymer, a propylene ethylene copolymer, or a blend of polypropylene and polyethylene. In any event, the maximum acceptable ethylene content is about 20% by weight of the ungrafted polypropylene component (2) of the blend.
- the graft copolymer component of the blend should contain from 0.1% to 2.5% maleic anhydride based on the total weight of the graft copolymer.
- a graft copolymer suitable for use in this invention as component (1) of the blend is sold by Hercules Chemical Company as Hercoprime A-35.
- the blend for coextrusion as layer 14, in the coextruded structure is from about 5% to about 30% by weight of the maleic anhydride grafted copolymer, and preferably about 5% to about 10%, and from about 70% to about 95% of the ungrafted polypropylene, preferably about 90% to about 95%.
- the overall maleic anhydride concentration in the blend layer 14, based on the entire blend composition is from about 0.005% to about 0.75%, with a preferred maleic anhydride concentration range of about 0.005% to about 0.25%.
- the components of the individual layers are fed into the infeed hoppers of extruders of like number, each extruder handling the material for one of the layers.
- each extruder may handle the two identical layers.
- the melted and plasticated streams from the individual extruders are fed into a multiple manifold coextrusion die.
- the layers are juxtaposed and combined in the die, and exit the die as a single multiple layer film of polymeric material.
- the polymeric material After exiting the die, the polymeric material is cast onto a first controlled temperature roll, passes around the first roll, and thence onto a second controlled temperature roll, which is normally cooler than the first roll.
- the controlled temperature rolls largely control the rate of cooling of the film after it exits the die.
- Typical operating temperatures for the first and second controlled temperature rolls are 160° F. and 120° F. respectively.
- a five-layer structure is coextruded, wherein similar 100 series numbers represent similar layers in FIG. 1.
- the entire structure is generally designated 110.
- Layers 112, 114, and 116 have the same compositions, and serve the same functions as layers 12, 14, and 16 respectively in FIG. 1.
- Layer 118 is a high gas barrier material such as EVOH.
- Layer 120 is a layer of nylon, and may be any nylon which may be coextruded with the gas barrier material.
- Hercoprime A-35 particles Five parts by weight of Hercoprime A-35 particles were blended with 95 parts by weight of pelletized Hercules SA-752 ungrafted polypropylene polymer to form the adhesive blend composition.
- a three layer film was cast coextruded through a 3-manifold cast die fed by three extruders processing, respectively, nylon 6, the above recited blend, and Hercules SA-752 polypropylene. Die temperature was 500° F. Line speed was 60 feet per minute. The film was cast onto a first controlled temperature chill roll maintained at 160° F., and passed from there onto a second chill roll at 120° F. The final film was 4.5 mils thick.
- the outer layers were 3.5 mils SA-752 polypropylene and 0.5 mil nylon, with a 0.5 mil layer of the blend serving as the adhesive layer between them.
- a three layer 4.5 mil film was cast coextruded as in EXAMPLE 1, using as the nylon layer a blend of 75% Nylon 6 and 25% Nylon 12.
- a three layer, 4.5 mil, film was cast coextruded as in EXAMPLE 1, using as the adhesive blend a composition of 10 parts by weight Hercoprime A-35 and 90 parts by weight SA-752.
- a three layer, 4.5 mil, film was cast coextruded as in EXAMPLE 2, using as the adhesive blend a composition of 10 parts by weight Hercoprime A-35 and 90 parts by weight SA-752.
- the three-layer stream was fed from the combining adaptor into the 3-manifold die, where it was juxtaposed, and finally, joined with the adhesive blend layer. Die temperature was 500° F.
- the final five-layer film was cast onto a first controlled temperature chill roll maintained at 160° F., and passed from there onto a second chill roll at 120° F. Line speed was 60 feet per minute.
- the final film was 5 mils thick and had the following distinct layers, in order:
- a five-layer, 5 mil, film was cast coextruded as in EXAMPLE 5, using, as the nylon layers, a blend of 75% Nylon 6 and 25% Nylon 12.
- a five-layer, 5 mil, film was cast coextruded as in EXAMPLE 5, using as the adhesive blend a composition of 10 parts by weight Hercoprime A-35 and 90 parts by weight SA-752.
- a five-layer, 5 mil, film was cast coextruded as in EXAMPLE 6, using as the adhesive blend a composition of 10 parts by weight Hercoprime A-35 and 90 parts by weight SA-752.
- the adhesive bond between layers 14 and 16 was measured as peel strength in pounds per one inch width strip of specimen.
- specimens were cut into one inch strips. They were then tested in a Chatillon tester, manufactured by John Chatillon and Sons, New York. Crossing head speed was 10 inches per minute.
- the resulting peel strengths of all the samples were 2 lbs./in. width, with a range of 1.8 to 2.1 lb./in. width.
Abstract
Description
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/635,631 US4617240A (en) | 1981-02-20 | 1984-07-30 | Coextruded film of polypropylene, polypropylene blend, and nylon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/236,601 US4361628A (en) | 1981-02-20 | 1981-02-20 | Coextruded film of polypropylene, polypropylene blend, and nylon |
US06/635,631 US4617240A (en) | 1981-02-20 | 1984-07-30 | Coextruded film of polypropylene, polypropylene blend, and nylon |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/417,674 Division US4552714A (en) | 1981-02-20 | 1982-09-13 | Process for producing coextruded film of polypropylene, polypropylene blend, and nylon |
Publications (1)
Publication Number | Publication Date |
---|---|
US4617240A true US4617240A (en) | 1986-10-14 |
Family
ID=26929940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/635,631 Expired - Lifetime US4617240A (en) | 1981-02-20 | 1984-07-30 | Coextruded film of polypropylene, polypropylene blend, and nylon |
Country Status (1)
Country | Link |
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US (1) | US4617240A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4668571A (en) * | 1986-05-02 | 1987-05-26 | The Dow Chemical Company | Coextrustion tie layer and process for producing such tie layer |
USH469H (en) | 1986-11-04 | 1988-05-03 | E. I. Du Pont De Nemours And Company | Clear plastic container with good gas and water vapor barrier properties |
US4910085A (en) * | 1985-11-29 | 1990-03-20 | American National Can Company | Multiple layer packaging films and packages formed thereof |
US4948016A (en) * | 1986-08-11 | 1990-08-14 | Sashco, Inc. | Laminated materials container |
EP0741160A1 (en) * | 1995-05-02 | 1996-11-06 | Wolff Walsrode Ag | Highly transparent deep drawable film having a sealable layer of polypropylene and linear low density polyethylene |
US6224956B1 (en) | 1990-05-17 | 2001-05-01 | Cryovac, Inc. | Breathable abuse resistant film for packaging cheese |
US6361843B1 (en) | 1997-09-22 | 2002-03-26 | Baxter International Inc. | Multilayered polymer structure for medical products |
US6562425B2 (en) | 1996-05-23 | 2003-05-13 | Pliant Corporation | Carrier release sheet for styrene molding process and process and system |
US20030159775A1 (en) * | 2001-01-29 | 2003-08-28 | Sum-Wing Tsui | Adhesive |
US6964798B2 (en) | 1993-11-16 | 2005-11-15 | Baxter International Inc. | Multi-layered polymer based thin film structure for medical grade products |
US20110068671A1 (en) * | 2009-09-23 | 2011-03-24 | Nuova Star S.P.A. | Combination of a hinge for doors or wings and a damping device |
US20140117046A1 (en) * | 2011-10-17 | 2014-05-01 | Sulzer Mixpac Ag | Cartridge, method of manufacturing same and multicomponent cartridge |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087587A (en) * | 1975-09-19 | 1978-05-02 | Chemplex Company | Adhesive blends |
US4190477A (en) * | 1978-01-04 | 1980-02-26 | American Can Company | Pouch |
US4233367A (en) * | 1977-01-06 | 1980-11-11 | American Can Company | Coextruded multilayer film |
US4361628A (en) * | 1981-02-20 | 1982-11-30 | American Can Company | Coextruded film of polypropylene, polypropylene blend, and nylon |
-
1984
- 1984-07-30 US US06/635,631 patent/US4617240A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087587A (en) * | 1975-09-19 | 1978-05-02 | Chemplex Company | Adhesive blends |
US4233367A (en) * | 1977-01-06 | 1980-11-11 | American Can Company | Coextruded multilayer film |
US4190477A (en) * | 1978-01-04 | 1980-02-26 | American Can Company | Pouch |
US4361628A (en) * | 1981-02-20 | 1982-11-30 | American Can Company | Coextruded film of polypropylene, polypropylene blend, and nylon |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4910085A (en) * | 1985-11-29 | 1990-03-20 | American National Can Company | Multiple layer packaging films and packages formed thereof |
US4668571A (en) * | 1986-05-02 | 1987-05-26 | The Dow Chemical Company | Coextrustion tie layer and process for producing such tie layer |
US4948016A (en) * | 1986-08-11 | 1990-08-14 | Sashco, Inc. | Laminated materials container |
USH469H (en) | 1986-11-04 | 1988-05-03 | E. I. Du Pont De Nemours And Company | Clear plastic container with good gas and water vapor barrier properties |
US6224956B1 (en) | 1990-05-17 | 2001-05-01 | Cryovac, Inc. | Breathable abuse resistant film for packaging cheese |
US6964798B2 (en) | 1993-11-16 | 2005-11-15 | Baxter International Inc. | Multi-layered polymer based thin film structure for medical grade products |
EP0741160A1 (en) * | 1995-05-02 | 1996-11-06 | Wolff Walsrode Ag | Highly transparent deep drawable film having a sealable layer of polypropylene and linear low density polyethylene |
US5935697A (en) * | 1995-05-02 | 1999-08-10 | Wolff Walsrode Ag | Highly transparent thermoforming film with a heat sealing layer based on polypropylene and linear low density polyethylene |
US6562425B2 (en) | 1996-05-23 | 2003-05-13 | Pliant Corporation | Carrier release sheet for styrene molding process and process and system |
US6576308B2 (en) * | 1996-05-23 | 2003-06-10 | Pliant Corporation | Carrier release sheet for styrene molding process and process system |
US6361843B1 (en) | 1997-09-22 | 2002-03-26 | Baxter International Inc. | Multilayered polymer structure for medical products |
US20030159775A1 (en) * | 2001-01-29 | 2003-08-28 | Sum-Wing Tsui | Adhesive |
US7037968B2 (en) | 2001-01-29 | 2006-05-02 | Glucd Ltd | Adhesive |
US20110068671A1 (en) * | 2009-09-23 | 2011-03-24 | Nuova Star S.P.A. | Combination of a hinge for doors or wings and a damping device |
US20140117046A1 (en) * | 2011-10-17 | 2014-05-01 | Sulzer Mixpac Ag | Cartridge, method of manufacturing same and multicomponent cartridge |
US10105731B2 (en) * | 2011-10-17 | 2018-10-23 | Sulzer Mixpac Ag | Cartridge, method of manufacturing same and multicomponent cartridge |
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Legal Events
Date | Code | Title | Description |
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STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
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AS | Assignment |
Owner name: AMERICAN CAN PACKAGING INC., AMERICAN LANE, GREENW Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:AMERICAN CAN COMPANY, A NJ CORP.;REEL/FRAME:004835/0338 Effective date: 19861107 Owner name: AMERICAN NATIONAL CAN COMPANY Free format text: MERGER;ASSIGNORS:AMERICAN CAN PACKAGING INC.;TRAFALGAR INDUSTRIES, INC. (MERGED INTO);NATIONAL CAN CORPORATION (CHANGED TO);REEL/FRAME:004835/0354 Effective date: 19870430 Owner name: AMERICAN CAN PACKAGING INC., CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AMERICAN CAN COMPANY, A NJ CORP.;REEL/FRAME:004835/0338 Effective date: 19861107 Owner name: AMERICAN NATIONAL CAN COMPANY, STATELESS Free format text: MERGER;ASSIGNORS:AMERICAN CAN PACKAGING INC.;TRAFALGAR INDUSTRIES, INC. (MERGED INTO);NATIONAL CAN CORPORATION (CHANGED TO);REEL/FRAME:004835/0354 Effective date: 19870430 |
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Owner name: PECHINEY PLASTIC PACKAGINC, INC., ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AMERICAN NATIONAL CAN COMPANY;REEL/FRAME:012463/0131 Effective date: 20011112 |
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Owner name: PECHINEY EMBALLAGE FLEXIBLE EUROPE, FRANCE Free format text: RESUBMISSION OF DOCUMENT ID NO 102198992;ASSIGNOR:PECHINEY PLASTIC PACKAGING, INC.;REEL/FRAME:013467/0484 Effective date: 20020117 |